Compositions for the preparation of cold-bleaching liquors,particularly active washing liquors

ABSTRACT

COMPOSITIONS USEFUL IN THE AQUEOUS COLD-BLEACHING OF TEXTILES COMPRISING (19 FROM 0.5% TO 95% BY WEIGHT OF AN ACTIVATOR FOR ACTIVE OXYGEN SELECTED FROM THE GROUP CONSISTING OF N-ACYL AND O-ACRYL COMPOUNDS HAVING 2 TO 9 CARBON ATOMS IN THE ACYL, SAID ACTIVATOR HAVING AN ACTIVATING ACTION OF AT LEAST 3 IN THE PER-ACID FORMATION TEST, (2) AT LEAST ONE COMPOUND SELECTED FROM THE GROUP CONSISTING OF (A) AN ALKALI METAL SESQUISILICATE OF THE RATIO ME2O:SIO2 OF 1 TO LESS THAN 2:1 IN AN AMOUNT THAT FROM 0.25 TO 3 ALKALI METAL ATOMS RE PRESENT PER ACYL GROUP IN SAID ACTIVATOR, AND (B) FROM 0 TO 20% BY WEIGHT OF A WATER-SOLUBLE SALT OF A PHOSPHORIC ACID ESTER SELECTED FROM THE GROUP CONSISTING OF PARTIAL ESTERS OF FATTY ALCOHOLS HAVING FROM 10 TO 22 CARBON ATOMS AND THEIR ETHOXYLATES AND PROPOXYLATES HAVING FROM 1 TO 10 ALKOXY UNITS WITH ORTHO PHOSPHORIC ACID, PYROPHOSPHORIC ACID AND POLYPHOSPHORIC ACID, AND (3) FROM 0 TO 97% BY WEIGHT OF OTHER CUSTOMARY INGREDIENTS OF BLEACHING AGENTS OF WASHING AGENTS HAVING A BLEACHING EFFECT.

US. Cl. 252-99 15 Claims ABSTRACT OF THE DISCLOSURE Compositions useful in the aqueous cold-bleaching of textiles comprising (1) from 0.5% to 95% by weight of an activator for active oxygen selected from the group consisting of N-acyl and O-acyl compounds having 2 to 9 carbon atoms in the acyl, said activator having an activating action of at least 3 in the Per-Acid Formation Test, (2) at least one compound selected from the group consisting of (a) an alkali metal sesquisilicate of the ratio Me O:SiO of 1 to less than 2:1 in an amount that from 0.25 to 3 alkali metal atoms are present per acyl group in said activator, and (b) from to 20% by weight of a Water-soluble salt of a phosphoric acid ester selected from the group consisting of partial esters of fatty alcohols having from to 22 carbon atoms and their ethoxylates and propoxylates having from 1 to 10 alkoxy units, with ortho phosphoric acid, pyrophosphoric acid and polyphosphoric acid, and (3) from 0 to 97% by weight of other customary ingredients of bleaching agents or washing agents having a bleaching effect.

THE PRIOR ART It is known to use aqueous solutions of hydrogen peroxide or of percompounds, yielding hydrogen peroxide in water, as oxidation and bleaching baths, particularly for fibrous substances and preferably for textiles. These bleaching baths may also be solutions of bleaching washing auxiliaries or washing agents. In such aqueous solutions the active oxygen is effective generally only at temperatures of from 80 C. to 100 C.

It has also been proposed to use organic compounds that belong to certain types of N-acyl or O-acyl compounds, in such treatment baths as activators for the percompounds. These activators transform the hydrogen peroxide present in the washing liquor into an organic peracid. By the process, the active oxygen is liberated at substantially lower temperatures of, for instance, C. to 70 0., preferably C. to 60 C., in a bleaching active state.

Unfortunately, however, it was found that the bleaching baths containing N-acyl or O-acyl activators had undesirable side efiects when utilized in the presence of copper such as is present in most washing equipment and, in addition, these bleaching baths containing N-acyl or O-acyl activators had an adverse effect on many optical brighteners also present in the treatment bath or on the treated textiles.

OBJECTS OF THE INVENTION An object of this invention is the development of compositions useful in the aqueous cold-bleaching treatment which overcome the drawbacks of the prior art compositions.

Another object of the present invention is the development of a composition useful in an aqueous cold-bleaching treatment consisting essentially of (1) from to 3,785,984 Patented Jan. 15, 1974 95% by weight of an activator for active oxygen selected from the group consisting of N-acyl and O-acyl compounds having 2 to 9 carbon atoms in the acyl, said activator having an activating action of at least 3 in the Per- Acid Formation Test, and (2) at least one compound selected from the group consisting of (a) an alkali metal sesquisilicate of the ratio Me O:SiO of 1 to less than 2:1 in an amount that from 0.25 to 3 alkali metal atoms are present per acyl group in said activator, and (b) from 0 to 20% by weight of a water-soluble salt of a phosphorus acid ester selected from the group consisting of partial esters of fatty alcohols having from 10 to 22 carbon atoms and their ethoxylates and propoxylates having from 1 to 10 alkoxy units, with orthophosphoric acid, pyrophosphoric acid and polyphosphoric acids.

A further object of the present invention is the development of a composition useful in an aqueous cold-bleaching treatment consisting essentially of (1) from 0.5% to 95 by weight of an activator for active oxygen selected from the group consisting of N-acyl and O-acyl compounds having 2 to 9 carbon atoms in the acyl, said activator having an activating action of at least 3 in the Per-Acid Formation Test, (2) at least one compound selected from the group consisting of (a) an alkali metal sesquisilicate of the ratio Me O:SiO of l to less than 2:1 in an amount that from 0.25 to 3 alkali metal atoms are present per acyl group in said activator, and (b) from O to 20% by weight of a water-soluble salt of a phosphorus acid ester selected from the group consisting of partial esters of fatty alcohols having from 10 to 22 carbon atoms and their ethoxylates and propoxylates having from 1 to 10 alkoxy units, with orthophosphoric acid, pyrophosphoric acid and polyphosphoric acids, and 3) from 0.1% to 97% by weight of at least one compound selected from the group consisting of (a) corrosion inhibitors selected from the group consisting of triazoles and tetrazoles, (b) organic sequestering agents for copper ions, (c) alkali metal builder salts, (d) percompounds giving H 0 in aqueous solutions and stabilizers for per-compounds, (e) tensides selected from the group consisting of anionic surface-active compounds, nonionic surface-active compounds and amphoteric surface-active compounds, (f) optical brighteners, (g) watersoluble organic builder salts, (h) antimicrobial agents, (i) soil suspension agents, (j) enzymes, (k) foam stabilizers, (l) non-surface-active foam inhibitors, (m) textile softeners and (11) water.

These and other objects of the invention will become more apparent as the description thereof proceeds.

DESCRIPTION OF THE INVENTION The invention relates to agents for the preparation of cold-bleaching liquors, particularly of cold-bleaching ac tive washing liquors.

These agents are characterized in that they contain (1) from 0.5 to 95 by weight of a N-acyl or O-ocyl compound serving as an activator for H 0 or percompounds that yield H 0 in aqueous solutions, having an activation value determined by the below described Per-Acid Formation Test of at least 3, preferably of at least 4.5; (2) as well as at least one of the following two compounds: such amounts of an alkali metal silicate of the composition Me O:SiO =l 2:1, that per acyl group of the activator at most 3 alkali metal atoms are present, 0 to 20% by weight of water-soluble salts of partial esters of fatty alcohols with 10 to 22, preferably 16 to 18 carbon atoms or their ethoxylation and/or propoxylation products, containing l to 10 glycolether groups in the molecule, with ortho-, pyroor polyphosphoric acids, (3) from 97% to 0, preferably to 40% by weight of other customary ingredients of bleaching agents or bleaching washing agents.

The named phosphoric acid esters are derived preferably from fatty alcohol derivatives, containing 2 to 6 glycolether groups in the molecule.

For reasons of simplification in the following, by activators, the above-mentioned N-acyl or O-acyl compounds with the activation value given there are understood; the above defined alkali metal silicates are called "sesquisilicates and the above defined partial esters of the ortho-, pyroor polyphosphoric acid are called phosphoric acid esters. If there are no phosphoric acid esters present, the amount of sesquisilicates should be at least such as 0.25 alkali metal atoms are present per acyl group of the activator. If, however, the invention products contain no sesquisilicates, the phosphoric acid esters should be present in amounts of at least 0.5% by weight of the total composition. Other silicates, that is such that contain less than 1 Me O per SiO may be present in the products of the invention, in addition.

The technical teaching, according to the invention, is based on the determination that both the sesquisilicates and the phosphoric acid esters, used alone or in combination, were found to be capable of eliminating certain undesired side effects, caused by the activators. These side effects appear above all in the presence of copper ions in the washing liquor. These copper ions may be naturally present in the water or may come from the copper heating bars of the washing machine. These copper ions impair, as was found in addition, above all in the presence of activators, the effect of the optical brighteners present in the washing liquor or in the fabrics to be washed, particularly those optical brighteners with an =NH-bonding. These optical brighteners may be present in the agents themselves, utilized for the prepartion of the cold-bleaching liquors, but also in the use of agents without optical brighteners, undesirable effects may occur, since by far the majority of the textiles, washed at home or in commercial plants, are repeatedly washed and may be loaded with optical brighteners from the textile finishing or from an earlier laundering in a washing liquor containing optical brighteners. Finally, the agents of the invention, not containing optical brighteners, may be used as special products in the home or in commercial plants together with washing agents or with washing ingredients, that contain per-compounds and optical brighteners, but no activators. The products of the invention warrant in this way a satisfactory washing result, also if the composition of the washing agents or washing agent ingredients with which they are utilized together is not compounded for the simultaneous presence of activators.

If the effect desired by the practice of the invention is based on the presence of sesquisilicates," the composition of the agents, according to the invention, lies generally within the frame of the following formula:

3% to 100%, preferably 10% to 80% by weight of an activator-alkali system consisting of (a) an N-acyl or O-acyl compound, serving as an activator for H or for a percompound yielding H 0 in an aqueous solution, that possesses an activation value, determined by the below described testing method, for the percompound of at least 3, preferably of at least 4.5.

(b) such amounts of an alkali metal sesquisilicate, that 0.25 to 3, preferably 0.5 to 1.5 alkali metal atoms are present per acyl group of the activator,

0 to 20%, by weight of customary additives for bleaching baths containing per-compounds, such as stabilizers, sequestering agents and anti-corrosion agents,

97% to 0, preferably 90% to 40% by weight of other customary ingredients of bleaching agents or bleaching washing agents.

The advantageous effect of the sesquisilicates can be increased if the agents, according to the invention, contain at least one of the following substances in the given amounts:

0 to 5%, preferably 0.1% to 2% by weight of corrosion inhibitors of the triazole and/or tetrazole types, that contain a =NMe or =NOMe group, in which Me is a metal or a hydrogen atom replaceable by metal,

0 to 20%, preferably, 1% to 10% by weight of the above defined phosphoric acid esters,

0 to 10%, preferably, 0.1% to 7% by weight of organic builder salts capable of sequestering copper.

Products not containing percompounds, that consist substantially of the activators, sesquisilicates and the further additions, according to the above definitions, are suitable for the use in the textile industry or in commercial laundries, where they are utilized together with hydrogen peroxide or with solid per-compounds as well as optionally conventional additives for the preparation of the bleaching or washing liquors. Such products may also be used, preferably in the form of packets in the desired application amounts or in the form of tablets, at home for the combined application with bleaching washing agents, free of activators. Such products often contain, besides the activator-alkali system and the other additives, also certain amounts of neutral and preferably alkalinereacting builder salts customary in washing auxiliaries and washing agents, so that their composition lies approximately within the range of the following formula:

20% to preferably 30% to 70% by weight of the above described activator-alkali system,

0 to 25%, preferably 0.1% to 15% by weight of the above described phosphoric acid esters, corrosion inhibitors and sequestering agents for copper,

80% to 10%, preferably 70% to 30% by weight of neutral or preferably alkaline-reacting builder salts customary in washing auxiliaries and washing agents as well as, optionally, of tensides.

Of course, also per-compounds yielding H 0 in aqueous solution may be incorporated into the agents of the invention for the preparation of cold-bleaching liquors, particularly of cold-bleaching active washing liquors. The composition of such bleaching products lies then approximately in the range of the following formula:

3 to by weight of a bleaching component, consisting of the activator-alkali system and such amounts of at least one per-compound, yielding H 0 in aqueous solution, that per gm.-atom of active oxygen at least 0.1 and at a maximum 4, preferably at least 0.2, and at a maximum 2 mols of activator are present,

0 to 25%, preferably 0.1% to 15% by wei ht of phosphoric acid esters corrosion inhibitors and/or sequestering agents for copper,

97% to 0, preferably 80% to 15% by weight of neutral or preferably alkaline reacting builder salts as well as, optionally, of tensides.

Both the special products intended preferably for the textile industry or for the commercial laundries and the soaking, pre-wash and washing agents intended preferably for home use fall under the above formulation.

The special products for commercial use contain mostly more than 40% by weight of per-compounds and activators, where this amount relates to the pure activator and to the pure per-compound, without sesquisilicates, corrosion inhibitors and sequestering agents. Of course, such products may also be used at home for special purposes, for instance as soaking or Washing agents with increased bleaching eifect, that may be of interest as coldwashing agent, or as bleaching rinsing agent for the Washed laundry. Such special products often contain no brighteners.

The products, to be used as soaking, pre-wash and washing agents for home use, contain mostly lesser amounts of per-compounds and activators. These are present mostly in amounts of from 3% to 40%, preferably of from 10% to 35% by weight. In addition, in these agents alkalinereacting, non-sequestering builder salts, sequestering builder salts as well as mostly tensides, are present as further ingredients in substantial amounts. If excess amounts of sesquisilicates are present in the activator-alkali system, they act as alkaline builder salts. The above defined phosphoric acid esters are simultaneously tensides and may, for this reason, also be present in larger amounts than given in the above formula. The same goes accordingly for the sequestering agents for copper which are ordinarily sequestering or complex-forming builder salts. For this reason, in the following formulaiton for the composition of soaking, pre-wash and washing agents, the sesquisilicates are assigned to the alkaline builders, the above defined phosphoric acid esters to the tensides, and the sequestering agents for copper to the sequestering builder salts.

Products that contain the combination, according to the invention, of activators, per-compounds and sesquisilicates as well as, optionally, corrosion inhibitors and sequestering agents, may also be used as soaking agents, particularly if the laundry remains for a longer time in the solutions of the soaking agents. Such soaking agents have approximately the following composition:

to by weight of tensides, including the optionally present phosphoric acid esters,

97% to 55% by weight, preferably 90% to 60% by weight, of preferably alkaline-reacting builder salts, including the sesquisilicates and the optionally present sequestering agents for copper,

3% to 40% by weight, preferably to 35% by weight of activators and per-compounds.

In addition, the below described washing agent ingredients, mostly used in smaller amounts, may be present in such soaking agents, such as anti-microbial acting compounds, soil suspension agents, optical brighteners, enzymes, perfumes, dyes, etc.

A preferred application field of the invention are the the cold-bleaching pre-washing and washing agents, whose composition lies generally in the range of the following formula:

5% to 40%, preferably 7% to 30% by weight of a tenside component, containing at least one tenside from the type of the sulfonates, sulfates, soaps, nonionics and/or of the phosphoric acid esters as well as, optionally, one or more of the following substances:

0 to 10%, preferably 0.5% to 8% by weight of foam stabilizers,

0 to 10%, preferably 0.5% to 8% by weight of non-surface-active foam inhibitors,

10% to 92%, preferably 30% to 70% by weight of sequestering and/or non-sequestering builder salts, including the sesquisilicates as well as optionally present sequestering agents for copper, whereby at least a part of these builder salts react alkaline, and whereby the amount of the alkaline to neutral-reacting builder salts preferably amounts to 0.5 to 7 times, and particularly 1 to 5 times the amount of the total tenside component,

3% to 40%, preferably 10% to 35% by weight of percompounds, yielding H 0 in aqueous solution, as well as activators for them, according to the above definition,

0 to 20%, Preferably 2% to by weight of other washing agent ingredients, such as textile softeners, corrosion inhibitors, anti-microbial active compounds,

soil suspension agents, optical brighteners, enzymes,

perfumes, dyes, water.

Fine washing agents, to be applied at temperatures up to 70, whose tenside content is mostly in the range of from 8% to 40%, preferably 12% to 40% by weight, also fall within this general formulation. Insofar as these fine washing agents are not intended for use in washing machines, particularly in drum-washing machines, they need not contain foam inhibitors.

Of particularly practical significance are the washing agents, intended for the use in washing machines, preferably in drum washing machines, in which the tenside component amounts mostly to 7% to 30% by weight. The tenside component contains mostly at least one of the three following tenside types in the amounts given:

15% to 99%, preferably 35% to by weight of sulfonates and/or sulfates with preferably 8 to 18 carbon atoms in the hydrophobic moiety.

10% to 60%, preferably 10% to 50% by weight of nonionic surface-active compounds,

1% to 60%, preferably 3% to 50% by weight of phosphoric acid esters as well as, optionally, one or several of the following compounds:

5% to 70%, preferably 10% to 60% by weight of soap,

0 to 10%, preferably 0.5% to 8% by weight of foam stabilizers,

0 to 10%, preferably 0.5% to 8% by Weight of non-surface-active foam inhibitors,

whereby, however, the foaming power of the tenside components are reduced either by the simultaneous presence of different tensides, diminishing reciprocically the foaming power and/or of foam reducing soap and/or of non-surface-active foam inhibitors.

If, however, the intended effect, according to the invention, is based only on the above defined phosphoric acid esters, that is, if the agents do not contain sesquisilicates, the phosphoric acid esters are present in amounts of from 0.5% to 20%, preferably 1% to 10% by weight of the total agent. In general from 1% to 5% by weight of these phosphoric acid esters are sufficient to attain the intended effect, according to the invention. Of course, alkali metal silicates that contain less than one alkali metal dioxide per silicon dioxide may be present.

These agents may represent soaking agents or special products for the home, for industrial plants or for the textile industry, that are utilized together with per-compounds, or with washing agents containing percompounds. They can contain the above defined phosphoric acid esters or other anionic tensides, whereby, however, the amount of these other anionic tensides, present together with the phosphoric acid esters, is not greater than 5% by weight. Occasionally, such products contain also nonionics and this amount is mostly not larger than 10% by weight, where, however, the total amount of the tenside lies mostly not over 20%, and preferably not over 10%, by weight. This is particularly valid for products that contain both activators and per-compounds, whereby these two ingredients together amount mostly to 35% to 75%, preferably 40% to 70% by weight of the whole agent.

The agents, according to the invention, which are free of sesquisilicates, also are utilizable as washing agents. In this case, the phosphoric acid esters, present in amounts of from 0.5% to 20%, preferably 1% to 10% by weight of the whole product, are to be considered as part of the tenside component.

The activators, to be used according to the invention should have, according to the above definition, an activation value of at least 3, preferably of at least 4.5 in the Per-Acid Formation Test.

PER-ACID FORMATION TEST The activation value (=titre) for the activators is determined in the following way:

Solutions which contain 0.615 gm./ liter of (4 mmol/liter) and 2.5 gm./liter of Na P O -10H O, are heated to 60 C., and then are mixed with 4 mmol/liter of activator and maintained at the said temperature for 5 minutes with stirring. Then 100 ml. of this liquid is added to a mixture of 250 gm. of ice and 15 ml. of glacial acetic acid and titrated immediately after addition of 0.35 gm. of potassium iodide with 0.1 N sodium thiosulfate solution, using starch as indicator. Under the given experimental conditions, for a 100% activation of the peroxide used, 8.0 m1. of thiosulfate solution are consumed, the titre is 8.0. This maximum value is of course seldom attained. Good activators have a titre of at least 4.5, preferably from to 7. Useful results are often obtained with activators having a titre of at least 3.0.

Activators of the N-acyl or O-acyl compounds type contain an acyl residue RCO, in which R represents optionally substituted hydrocarbon residues with 1 to 8 carbon atoms. If the residues R are aliphatic, they preferably have 1 to 3 carbon atoms, and if they are aromatic, they may contain up to 8 carbon atoms. Consequently, the residue R is preferably one of the following: lower alkyl, such as methyl, ethyl, n-propyl or isopropyl; phenyl; alkylphenyl such as toluyl or xylyl residues. Suitable substituents are C alkoxy groups, halogen atoms, nitro or nitrile groups; when R is an aromatic residue it may be chloroand/or nitro-substituted, especially m-chloro or mor p-nitro-substituted. Such substituents are, for example, chloroalkyl having 1 to 3 carbon atoms, m-chlorophenyl, p-nitrophenyl, and p-methoxyphenyl.

Of the activators described below, compounds with a melting point of at least 70 C., preferably at least 100 C. and especially at least 150 C., are specially suitable. Further the equivalent Weight of these compounds should be not more than 170, preferably not more than 130 and especially not more than 110 (the equivalent weight is here the quotient of the molecular weight and the number of RCO residues present in the molecule where the compound is N-acylated or O-acy1ated.).

The types of compound mentioned under (a) to (j) are useful activators according to the invention. In the formulae the numbered residues R have the meaning given for R above unless specifically otherwise indicated. If several residues R are present in a molecule, they may be the same or different.

(a) N-diacylated amines of the Formula I, in which X represents a residue R or one of the residues Ia, Ib, or Ic.

From this class of compounds, N,N,N,N'-tetraacetylmethylenediamine (melting point 9295 C.), N,N,N', N-tetraacetylethylenediamine, N,N diacetylaniline and N,N-diacetyl-p-toluidine are named as examples.

(b) N-alkyl-N-sulfonyl-carbonamides of Formula H, in which R preferably signifiies a C; alkyl residue.

Activators of this type are, for example, N-methyl-N- mesylacetylamide (melting point 73 -79 C.), N-methyl- N mesyl benzoylamide (M.P. 116118.5 C.), N methyl-N-mesyl-p nitrobenzoylamide (M.P. 159160 C.) and N methyl N mesyl-p-methoxybenzoylamide (M.P. 117-117.5 C.).

(c) N-acylhydantoins of Formula III, in which at least one of the residues X and X represent an -R-CO residue, while the other may also represent a residue R or a carboxymethyl or a lower alkoxycarbonylmethyl residue; Y and Y represent hydrogen or alkyl residues with 1 or 2 carbon atoms.

(III) Suitable compounds are, for example, 1,3-diacety1-5,5- dirnethylhydantoin, 1,3 dipropionylhydantoin (M.P. 104.5 to 106 C.) and 3-benzoylhydantoin-l-acetic acid ethyl ester.

((1) Cyclic N-acylhydrazides of Formula IV, in which the two nitrogen atoms are part of a 5- or 6-membered hetero-ring from the group of maleic acid hydrazide, phthalic acid hydrazide, triazole or urazole.

N-C 0 R41 (IV) A suitable compound is, for example, mono-acetyl-maleic acid hydrazide.

(e) Triacyl-cyanurates of Formula VI Activators of this type are, for example,

O-benzoylN,N-succinyl-hydroxylamine (M.P. 137- O-acetyl-N,Nsuccinyl-hydroxylamine (M.P. 132- O-p-methoxybenzoyl-N,N-succinyl-hydroxylamine (M.P. 142-l45 C.), O-p-nitrobenzoyl-N,N-succinyl-hydroxylamiue (M.P. 212-215 C.) and O,N,N-triacetyl-hydroxylamine.

(h) N,N-diacyl-sulfurylamides of Formula VIH, in which R and R preferably represent C alkyl residues or aryl residues such as phenyl, while R and R preferably represent C alkyl residues, especially C alkyl residues.

Baa-C 0 o ("J-R (VIII) N,N'-dimethyl-N,N-diacetyl-sulfurylarnide (M.P. 58 to 60 C.) and N,N'-diethyl-N,N'-dipropionyl-sulfurylamide (M.P. 97 C.) may be mentioned as examples.

(i) 1,3-diacyl-4,S-diacyloxy-imidazolidines of Formula 1X, in which X represents hydrogen or R, and R and R represent hydrogen or R.

N O DB To these belong:

l,3-diformy1-4,S-diacetoxy-imidazolidine (M.P. 160- 1,3-diacetyl-4,5-diacetoxy-imidazolidine (MP. 139- 1,3-diacetyl-4,S-dipropionyloxy-imidazolidine (MP.

(j) Acylated glycolurils of the general Formula X, in which X represents the residue R or RCO.

N- C H-IL RIM- O O JJ-Rroz Tetraacylated glycolurils and especially tetraacetylglycoluril (M.P. 233240 C.) are preferably used. In addition, the following acylated glycolurils are suitable:

di-(chloroacetyl)-diacetyl-glycoluril (M.P. 267-269 C.), tetrapropionyl-glycoluril (M.P. 144-l46 C.), 1-methyl-3,4,6-triacetylglycoluril (M.P. 179l80 C.), diacetyl-dipropionylglycoluril (M.P. 144-146 C.) and diacetyl-dibenzoyl-glycoluril (M.P. 244 249 C.)

The acylated glycolurils are not only of special practical importance on account of their excellent properties as activators, but owing to their high melting point they are very suitable for the preparation of pulverulent products which are stable on storage.

It is often sufficient to activate only a part of the active oxygen present. For this, addition of activator of at least 0.1, preferably of at least 0.2 mol of activator per gram-atom of active oxygen are sufficient. 'If the greatest possible activation of the active oxygen is required, the addition of activator can be increased up to 4 mols, preferably up to 3 mols. However, it is preferred to work with 0.3 to 2 mols of activator per gram-atom of active oxygen, These amounts can, of course, be varied according to the activity of the particular activator used.

The activators may be provided with a coating of substances which are inert towards the activators. This prevents a contact of the activators with the strongly alkaline-reacting alkali metal silicates, according to the above definition, and possibly with the percompounds, which contributes to the stability in storage of the products of the invention.

The alkali metal silicates contained in the products of the invention of the composition Me O:SiO =1 to less than 2:1 (Me-alkali metal) are mostly present as sodium or potassium silicates. Appropriately, an alkali metal silicate of the composition 1.5 Me O to 1 SiO is used. Silicates of this composition are known as sesquisilicates. For this reason, the alkali metal silicates, to be used according to the invention, of the composition of l to less than 2 Me O to 1 SiO, are called for the sake of simplicity 10 and to differentiate them from other alkali metal silicates, sesquisilicates.

Preferably, such sesquisilicates are utilized that have already been melted in the ratio MeO:SiO in which they are also applied. However, in addition to these, according to the invention, also sesquisilicates are utilized that were adjusted in aqueous solution from alkali metal silicates richer in SiO by addition of an alkali metal hydroxide to give the desired ratio of Me O:SiO and then were transformed to a dry powder. The effect of these silicates, however, cannot always be compared with the effect of the silicates named above as preferable.

If, as an activator, tetraacetylglycoluril and, as sesquisilicate, the compound 1.5 Na O.1SiO are utilized, per one part by weight of the activator, 0.66 part by weight of the silicate are required, in order that for each acetyl radical, one alkali metal atom is present.

The higher fatty alcohols or their ethoxylation products, used for the preparation of the ortho-, pyroor polyphosphoric acid partial esters, are substantially the same as are also used for the preparation of other tensides. In this connection, the following enumeration of the synthetic tensides, optically contained in the products of the invention are to be considered.

These phosphoric acid esters may be prepared according to various known procedures, such as by direct esterification of the alcohol component with the corresponding acids of phosphorus, with the halogen derivatives of phosphorus or with the corresponding phosphoric acid anhydrides, particularly with phosphorus pentoxide.

Above all the last-named reaction represents a practically useful preparation method for such esters. By this reaction, in addition to the partial esters of ortho-phosphoric acid also partial esters of anhydric acids of phosphorus are formed, particularly of the pyroand polyphosphoric acids, where, however, the esters of orthophosphoric acid, optionally also the esters of orthoand pyro-phosphoric acids represent the main product. The salts of the partial esters of the named acids, to be used according to the invention, may contain on each phosphorus atom, one or two higher fatty alcohol radicals bound as an ester. Often in the transesterification of fatty alcohols or of their alkoxylation products, mixtures of esters are formed with one or with two alcohol radicals per phosphorus atom.

Preferably, the partial esters of phosphoric acid of the invention have the formula wherein A is a member selected from the group consisting of hydrogen and Lal.

with the proviso that one A may be hydrogen, R is a member selected from the group consisting of hydrogen and methyl, R is a fatty alcohol residue having from 10 to 22 carbon atoms, n is an integer from 0 to 10. These partial esters of phosphoric acid are utilized in the form of their water-soluble salts, especially their alkali metal and ammonium salts where the hydrogen of A is replaced by alkali metal or ammonium, or their mono-, dior triethanolamine salts.

The salts of orthophosphoric acid diesters of ethoxylated fatty alcohols, with 2 to 6 ethyleneglycolether radicals in the molecule, for instance as obtained from coconut, palm kernel or tallow fatty acids, with 12 to 18 carbon atoms in the fatty alcohol radical have been proven particularly useful.

These partial esters of phosphoric acids also have tenside properties and may, therefore, be utilized in larger amounts as such than would be necessary from the point of view of corrosion protection.

The organic sesquestering agents for copper include the Water soluble, preferably alkali metal salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and amino-tri-ethylidene-diphosphonic acid. In their place also other sequestering agents for copper may be used, insofar as their sequestering power is not substantially below of that of the named compounds.

The named sequestering agents for copper have already been recommended as organic builder salts for soaking, prewashing and washing agents. For this reason, the above application amounts for these sequestering agents are only valid in the case that not already larger amounts of such sequestering agents are present as organic builder salt.

Triazoles and tetrazoles, known as anti-corrosion agents, with the groups :=NMe or =NOMe, are the following compounds, for instance, benzotriazole, methylbenzotriazole, 1,2- and 1,8-naphthotriazoles, nitrobenzotriazole, tetrazole, S-aminotetrazole, alkylene-5,5'-ditetra zole, -alkylenetetrazoles, 5-dialkyl-aminotetrazoles, and 5-alkyl-4-hydroxytetrazoles, where the alkyl or alkylene radicals may contain 1 to 5 carbon atoms.

Triazoles that contain an aromatic nucleus, such as a benzeneor naphthalene nucleus, are particularly effective. For this reason, for the practical application benzotriazole and the naphthotriazoles are preferred.

Of the preferably inorganic, per-compounds yielding H 0 in aqueous solution, sodium perborate tetrahydrate (NaBO -H O -3H O) is of special practical importance. Partly or completely dehydrated perborates, i.e., up to NaBO -H O may be used in its place. Borates such as NaBO -H O described in German Pat. 901,287 and U.S. Pat. 2,491,789, in which the ratio NaO:B 0 is less than 0.5 :1 and preferably lies in the region of 0.4 to 0.15:1, while the ratio H O :Na lies in the region of 0.5 to 4:1 are also useful. All these perborates may be wholly or partly replaced by other inorganic per-compounds, especially by peroxyhydrates, such as the peroxyhydrates of ortho-, pyro or polyphosphates, especially of the tripolyphosphates, as well as the carbonates.

It is advisable to incorporate in the compositions from 0.25% to by weight of the usual water-soluble and/ or water-insoluble stabilizers for the stabilization of the per-compounds. Suitable water-insoluble per-compound stabilizers which, for example, constitute 1% to 8%, preferably 2% to 7%, of the weight of the total preparation, are the magnesium silicates (MgO:SiO =4:1 to 1:4, preferably 2:1 to 1:2 and especially 1:1), mostly obtained by precipitation from aqueous solutions. Other alkaline earth metal, cadmium or tin silicates of corresponding composition are utilizable in their place. The above-mentioned organic sequestering agents for copper are useful as water-soluble per-compound stabilizers.

The optical brighteners, usable according to the invention, whose effect is impaired by slight amounts of copper ions, persent in aqueous solution, are all those with =NH-bridges. Particularly important representative of this type are the diaminostilbene sulfonic acid derivatives of the general formula wherein R and R may represent halogen atoms, lower alkoxy groups, the amino group or radicals of aliphatic, aromatic or heterocyclic primary or secondary amines as well as radicals of aminosulfonic acids where the aliphatic radicals, present in the above groups, contain preferably 1 to 4, and particularly 2 to 4 carbon atoms, while the heterocyclic ring systems are primarily rings with 5 to 6 members. As aromatic amine radicals preferably aniline, anthranilic acid or anilinesulfonic acid are of interest. Brighteners derived from the diaminostilbene sulfonic acids are mostly used as brighteners for cotton. The following products, derived from Formula I, are commercially available, where R represents the residue Some of these brighteners are, in regard to their fiber affinity, to be considered as transitional types to the polyamide brighteners, such as the brightener with To the cotton brighteners of the diaminostilbene sulfonic acid type also belongs the compound 4,4-bis-(4-phenylvicinal-triaZolyl-2) stilbene disulfonic acid-2,2.

These optical brighteners are present in the products of the invention, particularly in the washing agents, according to the invention, generally in amounts of from 0.05% to 1.5%, preferably from 0.07% to 1% by weight.

The products of the invention can be prepared by all procedures, customary in the production of oxidizing agents, bleaching agents, washing auxiliaries and washing agents. For instance, the single ingredients can be mixed with each other in a dry, powdery or granular state. These mixtures can be granulated or agglomerated, according to known processes, by spraying them, while being agitated, with water or with aqueous solutions containing active substances. This process is above all recommended when anhydrous salts are present in the mixture that crystallize with binding of water crystallization.

In all these processes it is recommended to avoid a direct contact of the activators and percompounds in the presence of water, since the activator eifect already takes place at that time, and a part of the activators or of the active oxygen is consumed.

This is particularly valid for the heat-drying processes, customary in the production of washing auxiliaries and washing agents. Mostly only those ingredients are incorporated into the aqueous charge to be heat-dried, that are not changed by water and/or heat, and to admix the other ingredients to the thus obtained initial powder. In the process, it is immaterial for the effect of the combinations of the invention in which partial powder the single ingredients are present. Thus, for instance, the sesquisilicates, the phosphoric acid esters of optionally ethoxylated fatty alcohols and the sequestering agents can be incorporated, together with the other ingredients of the product, particularly of washing auxiliary or washing agents, into an aqueous charge and then by known processes, preferably by heat drying, transformed to a powder. This powder is then mixed with the other ingredients, sensitive to moisture and/or heat, such as the activators, the percompound and optionally other, for the same reason separately to be incorporated, ingredients, such as enzymes.

An enumeration of the other ingredients present in the products of the invention, particularly in the washing auxiliaries and washing agents, such as tensides, builders, soil suspension agents, enzymes, etc. follows.

The anionic, amphoteric or non-ionic tensides contain in the molecule at least one hydrophobic residue mostly containing 8 to 26, preferably 10 to 22 and especially 10 to 18, carbon atoms and at least one anionic, non-ionic or amphoteric water-solubilizing group. The preferably saturated hydrophobic residue is mostly aliphatic, but possibly also alicyclic in nature. It may be combined directly with the water-solubilizing group or through intermediate members. Suitable intermediate members are, for example, benzene rings, carboxylic acid ester or carboxylic acid amide groups, residues of polyhydric alcohols linked in ether or ester-like form, such as, for example, those of ethylene glycol, propylene glycol, glycerine or corresponding polyether residues.

The hydrophobic residue is preferably an aliphatic hydrocarbon residue with 10 to 18, preferably 12 to 18, carbon atoms but deviations from the preferred range of carbon atoms are possible, depending on the nature of the surface-active compound in question.

Soaps from natural or synthetic fatty acids, possibly also from resin or naphthenic acids, are utilizable as anionic detergent substances, especially when these acids have iodine values of not more than 30, and preferably of less than 10.

Of the synthetic anionic surface-active compounds, the sulfonates and sulfates possess special practical importance.

The sulfonates include, for example, the alkylaryl sulfonates, especially alkylbenzene sulfonates, which are obtained from preferably straight-chain aliphatic hydrocarbons having 9 to 15, especially 10 to 14 carbon atoms, by chlorinating and alkylating benzene or from corresponding terminal or non-terminal olefins by alkylation of benzene and sulfonation of the alkylbenzenes obtained. Further, aliphatic sulfonates are of interest, such as are obtainable, for example, from preferably saturated hydrocarbons containing 8 to 18 and preferably 12 to 18 carbon atoms in the molecule by sulfcchlorination with sulfur dioxide and chlorine or sulfoxidation with sulfur dioxide and oxygen, and conversion of the products thereby obtained into the sulfonates. As aliphatic sulfonates, mixtures containing alkene sulfonates, hydroxyalkane sulfonates and disulfonates are useful, which are obtained from terminal or non-terminal C and preferably C olefins by sulfonation with sulfur trioxide and acid or alkaline hydrolysis of the sulfonation products. In the aliphatic sulfonates thus prepared, the sulfonate group is frequently found attached to a secondary carbon atom; however, sulfonates with a terminal sulfonate group obtained by reaction of terminal olefins with bisulfite can also be used.

Furthermore, salts, preferably dialkali metal salts of m-sulfo-fatty acids, and salts of esters of these acids with monoor poly-hydric alcohols containing 1 to 4, and preferably 1 to 2 carbon atoms belong to the sulfonates to be used according to the invention.

Further useful sulfonates are salts of fatty acid esters of hydroxyethanesulfonic acid or dihydroxypropane sulfonic acid, the salts of the fatty alcohol esters of lower aliphatic or aromatic sulfomonoor di-carboxylic acids containing 1 to 8 carbon atoms, alkylglycerylether sulfonates and the salts of the amide-like condensation products of fatty acids or sulfonic acids with aminoethanesulfonic acid.

As tensides of the sulfate type are fatty alcohol sulfates, especially those prepared from coconut fat alcohols, tallow fat alcohols or oleyl alcohol. Useful sulfonation products of the sulfate type are also obtainable from terminal or non-terminal C olefins. Sulfated fatty acid alkylolamides or fatty acid monoglycerides, and sulfated alkoxylation products of alkylphenols (C alkyl), fatty which may contain in the molecule 0.5 to 20, preferably alcohols, fatty acid amides or fatty acid alkylolamides,

14 l to 8 and especially 2 to 4 ethylene and/or propylene glycol residues, also belong to this group of surfaceactive compounds.

Suitable anionic surface-active compounds of the carboxylate type are the fatty acid esters or fatty alcohol ethers of hydroxycarboxylic acids, and the amide-like condensation products of fatty acids or sulfonic acids with aminocarboxylic acids, for example, with glycolcoll, sarcosin or protein hydrolysates.

Then non-ionic surface-active compounds, here called non-ionics, for the sake of simplicity, include products which owe their solubility in water to the presence of polyether chains, amineoxide, sulfoxide or phosphineoxide groups, alkylolamide groups and very generally, to an accumulation of hydroxyl groups.

The products obtainable by addition of ethylene oxide and/or glycide to fatty alcohols, alkylphenols, fatty acids, fatty amines, fatty acid and sulfonic acid amides are of special practical interest. These non-ioinics may contain per molecule 4 to 100, preferably 6 to 40 and especially 8 to 20 ether residues, particularly ethylene glycol ether residues. Moreover, propylene or butylene glycol ether residues or polyether chains may be present in or at the ends of these polyether residues.

Further, products known by the trade name of Pluronics or Tetronics belong to the non-ionics. They are obtained from water-insoluble polypropylene glycols or from water-insoluble propoxylated lower aliphatic alcohols containing 1 to 8, preferably 3 to 6 carbon atoms and/or from water-insoluble propoxylated alkylenediamines. These water-insoluble (i.e. hydrophobic) propylene oxide derivatives are converted into the said nonionics by ethoxylation until they become soluble in water. Finally, the reaction products of the above-mentioned aliphatic alcohols with propylene oxide known as Ucon- Fluid some of which are still Water-soluble, are useful as non-ionics.

The non-ionics also include fatty acid or sulfonic acid alkylolamides which are derived, for example, from monoor di-ethanolamine, dihydroxypropylamine or other polyhydroxyalkylamines, for example the glycamines. They can be replaced by amides from higher primary or secondary alkylamines and polyhydroxyacrboxylic acids.

The surface-active amineoxides include, for example, the products derived from higher tertiary amines having a hydrophobic alkyl residue and two shorter alkyl and/or alkylol residues containing up to 4 carbon atoms, each.

Amphoteric surface-active compounds contain in the molecule both acid and basic hydrophilic groups. Carboxyl, sulfonic acid, sulfuric acid half ester, phosphonic acid and phosphoric acid partial ester groups are the acid groups. Basic groups include primary, secondary, tertiary and quaternary ammonium groups. Amphoteric compounds with quaternary ammonium groups belong to the betaine type.

Carboxy, sulfate and sulfonate betaines have particular practical interest on account of their good compatibility with other surface-active compounds. Suitable sulfobetaines are obtained, for example, by reacting tertiary amines containing at least one hydrophobic alkyl residue with sultones, for example propaneor butane-sultone. Corresponding carboxybetaines are obtained by reacting the said tertiary amines with chloracetic acid, or its salts or with chloracetic acid esters and splitting the ester linkage.

The foaming power of the surface-active compounds can be increased or reduced by combination of suitable types of surface-active compounds, just as it can be changed by additions of the non-surface-active organic substances.

Suitable foam stabilizers, above all in the case of surface-active compounds of the sulfonate or sulfate type, are surface-active carboxy or sulfo-betaines and also the above-mentioned non-ionics of the alkylolamide type.

Moreover, fatty alcohols or higher terminal diols can be utilized for this purpose.

Products with a reduced foaming power are primarily intended for use in washing and dishwashing machines, where sometimes a limited repression of foam is sufiicient while in other cases a stronger foam repression may be desired. Products which foam in the middle range of temperature up to about 65 C., but at higher temperatures (70 to 100 C.) develop less and less foam are of special practical importance.

A reduced foaming power is frequently obtained with combinations of different types of surface-active compounds, especially with combinations of synthetic anionic surface-active compounds, particularly of (l) sulfates and/or sulfonates or of (2) non-ionics on the one hand and (3) soaps on the other hand. With combinations of the components (1) and (2) or (1), (2) and (3), the foaming power can be affected by the particular soap used. The inhibition of foam is smaller with soaps from preferably saturated fatty acids with 12 to 18 carbon atoms, while a greater inhibition of foaming, particularly in the higher temperature range, is obtained by soaps from saturated fatty acid mixtures having 20 to 26, preferabl 20 to 22 carbon atoms, used in an amount of from 5 to by weight of the total soap fraction present in the combination of surface-active compounds.

The foaming power of the surface-active compounds can also be reduced, by the addition of known, non-surface-active foam inhibitors. These include optionally chlorine-containing N-alkylated aminotriazines, which are obtained by reacting 1 mol of cyanuric chloride with 2 to 3 mols of a monoand/or di-alkylamine having 6 to 20, preferably 8 to 18 carbon atoms in the alkyl residue. Aminotriazine or melamine derivatives which contain propylene glycol or butylene glycol ether chains, in an amount of 10 to 100 of such glycol residues per molecule, have a similar action. Such compounds are obtained, for example, by addition of corresponding amounts of propylene and/ or butylene oxide to aminotriazines, especially to melamine. The reaction products from 1 mol of melamine with at least 20 mol of propylene oxide or at least 10 mol of butylene oxide are preferred. Products which are obtained by addition of 5 to 10 mol of propylene oxide to 1 mol of melamine and further addition of 10 to 50 mol of butylene oxide to this propylene oxide derivative have proved particularly effective.

Other non-surface-active water-insoluble organic compounds, such as paraffins or halogenated parafiins with melting points below 100 C., aliphatic C to C ketones and aliphatic carboxylic acid esters, which contain at least 18 carbon atoms in the acid or alcohol residue, possibly also in both of these two residues (for example triglycerides or fatty acid-fatty alcohol esters), can be used as foam inhibitors, particularly in combinations of anionic synthetic surface-active compounds and soaps.

The non-surface-active foam inhibitors are frequently only completely effective at temperatures at which they are present in the liquid state, so that the foaming behavior of the products can be controlled by choice of suitable foam inhibitors in a similar way to that by the choice of soaps from fatty acids of suitable chain lengths.

When foam stabilizers are combined with foam inhibitors dependent upon temperature, good foaming products are obtained at lower temperatures which, as the temperature approaches the boiling temperature, foam less and less.

Suitable weakly-foaming non-ionics, which can be used both alone and in combination with anionic, amphoteric and non-ionic surface-active compounds and which reduce the foaming power of more strongly foaming surfaceactive compounds, are products of addition of propylene oxide to the above-described surface-active polyethylene glycol ethers as well as the also above-described Pluronic, Tetronic and Ucon-Fluid types.

Suitable builders are weakly acid, neutral and alkaline reacting inorganic or organic salts, especially inorganic or organic complex-foaming substances.

Useful, weakly acid, neutral or alkaline-reacting salts according to the invention are, for example, the alkali metal bicarbonates, carbonates, borates or silicates, mono, dior tri-alkali metal orthophosphates, dior tetraalkali metal pyrophosphates, alkali metal metaphosphates known as complex-forming substances, alkali metal sulfates and the alkali metal salts of organic, non-surface-active sulfonic acids, carboxylic acids and sulfocarboxylic acids containing 1 to 8 carbon atoms. These include, for example, water-soluble salts of benzene-, tolueneor xylene-sulfonic acid, water-soluble salts of sulfoacetic acid, sulfobenzoic acid or salts of sulfodicarboxylic acids and the salts of acetic acid, lactic acid, citric acid and tartaric acid.

Further, the water-soluble salts of higher molecular weight polycarboxylic acids are utilizable as builders, especially polymerizates of maleie acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, methylenemalonic acid and citraconic acid. Co-polymerizates of these acids with one another or with other polymerizable substances, as for example, with ethylene, propylene, acrylic acid, methacrylic acid, crotonic acid, 3-butenecarboxylic acid, 3- methyl-Z-butenecarboxylic acid and with vinyl methyl ether, vinyl acetate, isobutylene, acrylamide and styrene, are utilizable.

Suitable complex-forming builders are also the weakly acid reacting metaphosphates and the alkaline reacting polyphosphates, especially tripolyphosphate, in the form of their alkali metal salts. They may be wholly or partly replaced by organic complex forming substances.

The organic complex-forming substances, include, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid, polyalkylene-polyamine-N-polycarboxylic acids and other known organic complex-forming substances, while combinations of different complex-forming substances may also be used. Diand poly-phosphonic acids of the following constitutions also belong to the other known complex-forming substances:

in which R represents alkyl and R alkylene radicals with l to 8, preferably 1 to 4 carbon atoms, X and Y represent hydrogen or alkyl radicals with l to 4 carbon atoms and Z represents OH, NH or NXR. For a practical application above all the following compounds are considered: methylene-diphosphonic acid, l-hydroxyethane-l,l-diphosphonic acid, l-aminoethane-1,1-diphosphonic acid, aminotri-(methylene-phosphonic acid), methylamineor ethylamino-di-(methylene-phosphonic acid) as well as ethylenediamine-tetra- (methylene-phosphonic acid). All these complexing compounds may be present as free acids or preferably as the alkali metal salts.

Further, soil suspending agents or greying inhibitors may be contained in the preparations according to the invention, which hold the dirt loosened from the fiber suspended in the bath and thus prevent greying. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatine, salts of ether-carboxylic acids or ether-sulfonic acids of starch or cellulose or salts of acid sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acid groups are also suitable for this purpose. Furthermore, soluble starch preparations and 17 starch products other than those mentioned above can be used, for example, degraded starch, and aldehyde starches. Polyvinylpyrrolidone is also useful.

The constituents of the treatment compositions according to the invention, especially washing compositions and washing assistants of this kind, and particularly the builder substances, are usually chosen so that the preparations have a neutral to distinctly alkaline reaction, so that the pH value of a 1% solution of the preparations mostly lie in the region from 7 to 12.Fine washing compositions usually have a neutral to weakly alkaline reaction (pH value 7 to 9.5), while soaking, pre-washing and boiling washing compositions are adjusted to be more strongly alkaline (pH value 9.5 to 12, preferably 10 to 11.5). The action of the activators is combined with a certain consumption of alkali. Therefore, the builder substances present should should be in an amount sufficient to prevent the pH value from falling below the given minimum values during the whole period of treatment.

The enzymes to be used are mostly a mixture of different enzymic substances. They are called proteases, amylases, carbohydrases, esterases, lipases, oxidoreductases, catalases, peroxidases, ureases, isomerases, lyases, transferases, desmolases or nucleases, depending upon their action. The enzymic substances obtained from strains of bacteria or fungi such as Bacillus subtilis and Streptomyces griseus are of particular interest, especially protases or amylases. Preparations obtained from Bacillus subtilis have the advantage compared with others that they are relatively stable towards alkali, per-compounds and anionic detergent substances and are still active at temperatures up to 70 C.

Enzyme preparations are usually marketed by the manufacturers as aqueous solutions of the active substances or with the addition of diluents, as powders. Suitable diluents are sodium sulfate, sodium chloride, alkali metal ortho-, pyroor polyphosphates, especially tripolyphosphate. Frequently moist enzyme preparations are mixed with calcined salts, which then bind water of crystallization present and the enzymic substances, possibly with agglomeration of the particles to larger particles.

When the enzymic substances are present as dry powders, liquid, paste-like and possibly also solid, non-ionic. preferably surface-active, organic compounds, especially the above-described non-ionics, can be used at the usual room temperatures to bind the enzymes to the powders of the washing compositions or washing assistants. For this purpose a mixture of the respective product and the enzymic substance is preferably sprayed with the abovementioned non-ionic substances, or the enzyme preparations is dispersed in the said non-ionic substance and this dispersion is united with the other contituents of the product. When these other constituents are solids, the dispersion of the enzymic substances in the non-ionic component can also be sprayed on the other solid constituents.

The enzymes, or combinations of enzymes with different actions, are generally used in quantities such that the finished products have protease activitie of 50 to 5000, preferably 100 to 2500 LVE/ g. and/or amylases activities of 20 to 5000, preferably 50 to 2000 SKBE/g. and/or lipase activities of 2 to 1000, preferably 5 to 500 IE/g.

These data on enzyme activities result from the activities of those enzyme preparations which at the present time seem to be suitable from the economic standpoint for use in the washing composition field. From the chemical-technical standpoint the enzyme activities of the preparations can be increased as desired, so that the activities in the case of proteases and amylase may be raised, for example, up to five times, and in the case of lipases, for example, up to ten times, the highest values given above. If, therefore, in the future preparations with such high activities should be available which also economically appear appropriate for the use in the application fields,

named at the beginning, products with respective higher enzyme activities can be prepared.

With reference to the determination of the enzyme activities, the following literature references are given:

Determination of the activity of proteases according to Lohlein-Volhard:

A. Kunzel, Chemical Tanning Pocketbook, 6th ed.,

Dresden and Leipzig, 1955;

Determination of the activity of amylases:

J. Wohlgemuth, Biochemische Zeitschrift," vol. 9

(1908), pp. l-9;

R. M. Sandstedt et al., Cereal Chemistry, vol. 16

Determination of the activity of lipases:

R. Willstatter et al., Hoppe-Seylers Zeitschrift fiir Physiologiche Chemie, vol. 125 (1923), pp. 110- 117;

R. Boissonas, Helvetica Chemica Acta, vol. 31 (1948) The products according to the invention may also contain antimicrobial substances. As such, the Z-hydroxy- 2,4,4-trichloro-diphenylether has been proven good.

The following example illustrate the practice of the invention without being limitative in any respect.

EXAMPLES The salt-like constituents contained in the following, such as salt-like surface-active compounds, other organic salts as well as inorganic salts, are present as the sodium salts, unless otherwise stated. The expression and abbreviation used have the following meanings:

ABS is the salt of an alkylbenzene sulfonic acid with 10 to 15, preferably 11 to 13, carbon atoms in the alkyl chain, obtained by condensing straight-chain olefins with benzene and sulfonating the alkylbenzene thus formed.

Alkanesulfonate is a sulfonate obtained from paraffins with 12 to 16 carbon atoms by the sulfoxidation method.

HPK-sulfonate or HT-sulfonate are the sulfonates in the ot-position, obtained from the methyl esters of a hardened palm kernel fatty acid or a hardened tallow fatty acid by sulfonation with S0 Olefin sulfonate is a sulfonate obtained from mixtures of olefins with 12 to 18 carbon atoms by sulfonating with and hydrolyzing the sulfonation product with an alkaline liquor, which sulfonate consists substantially of alkenesulfonate and hydroxyalkanesulfonate, but contains in addition small quantities of disulfonates. Products are useful which have been made from ocor from non-terminal olefins.

KA-sulfate and TA-sulfate are the salts of sulfated substantially saturated fatty alcohols, prepared by reduction of coconut fatty acid and tallow fatty acid, respectively.

KA-EO-sulfate is the sulfated product of addition of 2 mols of ethylene oxide to 1 mol of fatty alcohol.

KA-EO-phosphate" or TA-EO-phosphate are the orthophosphoric acid diesters of the addition products of about 4 mols ethylene oxide to 1 mol of coconut or tallow alcohol. When these tensides are utilized as the diethanlamine or triethanolamine salts, the percentage figures in the table are marked by a (D) or (T), respectively.

OA+10 E0, KA-l-20 E0 or Fs-amido-i-S B0 are the addition products of ethylene oxide (E0) to technical oleyl alcohol (0A) or coconut alcohol (KA) or coconut fatty acid amide, respectively, where the numbers represent the molar amounts of ethylene oxide added to 1 mol of starting material.

KA+9 EO'+12 PO is a non-ionic obtained by reaction of 1 mol of KA-l-9 EO with 12 mols of propylene oxide.

Carboxybetaine or Sulfobetaine are the betaines obtained by reaction of 1 mol of coconut alkylidmethylamine with 1 mol of chloroacetic acid or with 1 mol of propanesultone, respectively.

CMC is the salt of carboxymethylcellulose.

NTA, EDTA, DETP, HEDP, or ATMP are the salts of nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethanediphosphonic acid or aminotrimethylene phosphonic acid, respectively.

The composition of fatty acid mixture from which the Soaps B, C and D was prepared, and the composition of fatty acid mixtures the Soap G which may be used instead of the other soaps, are seen from the following Table I.

Ingredients of the preparation NaBO H202 TAGU is tetraacetylglycoluril.

The sesquisilicate of the composition 1.5 Na O- ISiO' had been melted in this quantitative ratio.

The compositions of some agents, not containing percompounds, can be seen from the two following Tables 11 and III. The agents, designated as Al to A7, are to be considered as activator-alkali systems, that contain sesquisilicates, while the agents, marked with A8 to A12 are free of sesquisilicates. All these agents, A1 to A12, are applied in the home, in commercial laundries or in the textile industry together with percompounds or with conventional bleaching washing agents.

TAB LE 11 Percent by weight of ingredients in Example- A1 A2 A3 A4 A5 A6 A7 TAGU 31. O 30. 5 27. 42. 8 36. 6 19. 1 36. 1.5 NazO-1 SiOz 21.0 19. 5 l9. 2 26. 7 25. 6 12. 7 24. 3 KA-EO-phosphate 9. 3 18.0 (T) 5.2 (D) TA-EO-nhnsnhata 19 2 Benzotn'azole. 00. 2 Methylbenzotraizole- 1. 3 1,8-naphthotriazo1e- 1. 0. 6 Na4P2O1 38. 5 34. 6 22. 3 6. 1 NazCOa 50. 0 30. 5 36. 6 26. 6 27. 3

4 TABLE III 0 Percent by weight of ingredients in Example Ingredients of the preparation A8 A9 A10 A11 A12 KA-EO-phosphate. 4. 1 3. 4 (T) 5 4 (D) If the Soaps B, C and D in the formulations given below are replaced by the same quantity of the Soap G, washing compositions are obtained in which the foaming is somewhat less strongly inhibited than the corresponding composition with Soap C but somewhat less than with Soap B.

Together with these soaps or in place of them, nonsurfaoe-active foam inhibitors can be used, for example, a mixture of about of a di(alkylamino)-monochlorotriazine and about of a N,N,N"-trialkylmelamine. In all these triazine derivatives the alkyl residue may be present as mixtures of homologs with 8 to 18 carbon atoms. The monochlorotriazine derivative or trialkylmelamine can also be used with a similar result. Provided 'IA-EO-phosphate Na20-3.3 SiO3. NaaPaOm N11200:

1n the agents, according to Examples A8 to A12, as non-ionics the known non-ionic tensides can be used, particularly the E0 or EO-PO addition products, described in the introduction to the examples.

If it is desired that the agents, according to Examples A1 to A12, should have the property to sequester copper ions in addition 0.2% to 5% by Weight of EDTA, DETPA or ATMP are added with a corresponding reduction of the N34P2D7 and/or Na CO content.

The composition of some bleaching agents, according to the invention, that can preferably be applied in the 0 textile industry or in commercial laundries as bleaching components, can be seen from the following Examples B1 to B20 of Tables IV and V.

TABLE IV Percent by weight of the ingredients in Example Ingredients of the preparation B1 B2 B3 B4 B5 B6 B7 B8 B9 B10 Perborate (mono) 41. 0 22. 6 38. 1 34. 8 38.0 47. 1 32. 2 Perborate (tetra) 41. 0 36.1 43. TAGU 23. 0 19. 7 21. 3 23. 5 16. 5 23. 3 27. 3 22. 8 10. 1 24. 8 1.5 Nag-1 SiOz 16. 0 13. 6 13. 5 15. 2 12. 0 14. 9 17. 4 15. 0 6. 7 16. 5 KA-EO-phosphate.. 5.8 23.6 (T) 3 5 (D) 'IA-E O-phnsphate 0 EDTA 2.0 2.9 0.2 0.7 DETPA O. 5 ATMP 1. 6 Benzotriazole O. l Methylb enzo 0. 7 1,8-naphthotr1'a1ole NBAPZO TABLE IXContinued Percent by weight of ingredients in Example Ingredients of the washing agent W16 W17 W18 Sulfobetaina 0, 5 Foam inhibitor 0. Na P Om NazO-3.3 SiO2.

HEDP 0. 3 .ATMP-.. 1. 5 MgSiOa 2.3 2.5 2.0 1.4 Perborate (mono) 17. 0 10. 0 14 0 15. 6 Perborate (tetra) 19. 0 TAG 4.2 11.0 6.0 10.0 12.0 Brightener I 0. 25 0. 29 0. 25 0. 25 0. 29 Brightener III 0. 08

Brightener IV 0. 10

Residue water-..

In the use of the agents, according to the invention, described in the examples, the corrosion of machine construction parts made of copper or zinc is strongly reduced, and the brighteners are fully effective. The hydrolysis of the tripolyphosphate is no more than occurs in preparation of washing agents which are free of activator, so that no increased incrustations of mechanical parts and no increased incrustations of the washed textiles are observed.

If, in the agents of the Examples A1 to A12, B1 to B and W1 to W20, the tetraacetylglycoluril is replaced by the corresponding amounts of tetrapropionylglycoluril, methyl-triacetyl-glycoluril, diacetyl-dibenzoyl glycoluril, diacetylaniline, diacetyltoluidine, diacetyl-dimethylhydantoin, tetraacetyl-methylenediamine or tetraacetylethylenediamine, similar results are obtained, but the perborate is 3 better activated by the acylated glycolurils than by the other activators.

The preceding specific embodiments are illustrative of the practice of the invention. It is to be understood, however, that other expedients known to those skilled in the art or disclosed herein may be employed without departing from the spirit of the invention or the scope of the appended claims.

We claim:

1. A composition useful in an aqueous cold-bleaching treatment consisting essentially of (1) from 35% to 95% by weight of an activator for active oxygen, said activator having a melting point of at least 70 C. and an activating action of at least 3 in the Per-Acid Formation Test and being selected from the group consisting of (a) N-diacylated amines having the formula R-CO wherein R here and hereafter is a member selected from the group consisting of methyl, ethyl, n-propyl,

i-propyl, phenyl, tolyl, Xylyl and chloroalkyl having 1 to 3 carbon atoms and X represents a member selected from the group consisting of C 0-3. 0 0-K o OR R, CH;N CH;CH;N and N o OR O OR C 0R (b) N-alkyl-N-sulfonyl-carbonamides having the formula O CR21 ra-N S O-Rzz wherein R represents alkyl having 1 to 3 carbon atoms, R represents a member selected from the group consisting of R, p-nitrophenyl and p-methoxyphenyl and R represents R,

(c) N-acyl-hydantoins having the formula ai (iJO-(EYsz Xsg-N N-Xai wherein at least one of X and X is RC0 and the other is selected from the group consisting of RCO, R, carboxymethyl and carbethoxymethyl, and Y and Y are selected from the group consisting of hydrogen and alkyl having 1 to 2 carbon atoms, (d) cyclic-N-acyl-hydrazines having the formula wherein the two nitrogen atoms are part of a hetero ring selected from the group consisting of maleic hydrazide, phtnalic hydrazide, triazole, and urazole,

(e) triacyl-cyanurates having the formula wherein R has the above defined values, (f) phthalic acid anhydride and m-chlorobenzoic acid anhydride,

(g) O,N,N-trisubstituted hydroxylamines having the formula Rn-CO NO-C0(CHz)nR1a wherein R represents a member selected from the group consisting of R and COR7Q COON X and X represent members selected from the group consisting of RCO, RSO phenyl, tolyl, xylyl and, together with the corresponding R -CO and R -CO, succinyl and phthalyl, R and R represent members selected from the group consisting of R and, together with the corresponding X and X and the CO, succinyl and phthalyl, and n represents an integer from 0 to 2, (h) N,N-diacyl-sulfurylamides having the formula Ra: Ra: NSOzN B r-O0 COR34 wherein R and R represent alkyl having 1 to 3 carbon atoms and R and R represent alkyl having 1 to 4 carbon atoms and phenyl, (i) 1,3 diacyl 4,5 diacyloxy imidazolidines having the formula (lJO--R N CH-O-OOR 25 wherein X represents a member selected from the group consisting of R and hydrogen, and (1) acylated glycolurils having the formula wherein X represents a member selected from the group consisting of R-CO and R, and (2) at least one compound selected from the group consisting of (a) an alkali metal sesquisilicate of the ratio Me O:SiO of 1 to less than 2:1 in an amount that from 0.25 to 3 alkali metal atoms are present per acyl group in said activator, and (b) from to 20% by weight of a water-soluble salt of a phosphorus acid ester selected from the group consisting of partial esters of fatty alcohols having from to 22 carbon atoms and their ethoxylates and propoxylates having from 1 to 10 alkoxy units, with orthophosphoric acid, pyrophosphoric acid and polyphosphoric acids.

2. The composition of claim 1 containing from 0.5% to 20% by weight of said water-soluble salt of a phosphorus acid ester.

3. The composition of claim 1 containing said alkali metal sesquisilicate only.

4. The composition of claim 1 wherein said activator for active oxygen has the formula Rmr O 0 wherein R R and R represent a member selected from the group consisting of alkyl having 1 to 3 carbon atoms, phenyl, and phenylalkyl having 7 to 8 carbon atoms and X represents a member selected from the group consisting of R and R -CO.

5. The composition of claim 1 wherein said Watersoluble salt of phosphorus acid is present in an amount of from 1% to 10% by weight, said alkali metal sesquisilicate is present in an amount of from 0.4 to 1 part by Weight for each part by weight of said activator and further containing from 0.1% to 2% by weight of corrosion inhibitors selected from the group consisting of triazoles and tetrazoles, containing at least one group selected from the group consisting of =NMe and :NOMe where Me represents a member selected from the group consisting of a monovalent metal or a hydrogen atom replaceable by a monovalent metal and from 0.1% to 7% by weight of an organic sequestering agent capable of complexing copper ions.

6. The composition of claim 1 having a further content of from 30% to 70% by weight of said composition of alkaline-reacting inorganic builder salts.

7. A composition useful in an aqueous cold-bleaching treatment consisting essentially of (1) from 3% to 100% by Weight of a bleaching component consisting of the composition of claim 1 wherein said component (2) is said alkali metal sesquisilicate and such amounts of at least one inorganic per compound, yielding H 0 in aqueous solution, that per gram-atom of active oxygen, from 0.2 to 2 mols of said activator are present, (2) from 0 to by weight of a component consisting of from 0 to 10% by weight of the composition of said water-solublesalt of a phosphorus acid of claim 1, from 0 to 2% by weight of said composition of corrosion inhibitors selected from the group consisting of triazoles 26 and tetrazoles, containing at least one group selected from the group consisting of =NMe and :NOMe and Me represents a member selected from the group consisting of a monovalent metal or a hydrogen atom replaceable by a monovalent metal, and from 0 to 7% by weight of the composition of an organic sequestering agent capable of sequestering copper ions, and (3) from 0 to 97% by weight of alkaline-reacting inorganic builder salts.

8. The composition of claim 2 containing from 1% to 10% by weight of said water-soluble salt of a phosphorus acid ester.

9. The composition of claim 2 wherein said phosphorus acid ester has the formula wherein A is a member selected from the group consisting of hydrogen and with the proviso that one A may be hydrogen, R is a member selected from the group consisting of hydrogen and methyl, R is a fatty alcohol moiety having from 10 to 22 carbon atoms, and n is an integer from 0 to 10.

10. The composition of claim 9 wherein R is hydrogen and n is an integer from 2 to 6.

11. The composition of claim 3 wherein said ratio Mezolsiog is 1.511.

12. The composition of claim 4 wherein said activator for active oxygen is a member selected from the group consisting of tetraacetylglycoluril, tetrapropionylglycoluril, methyltriacetylglycoluril and diacetyldibenzoylglycoluril.

13. The composition of claim 4 wherein said alkali metal sesquisilicate has a ratio Me O:SiO of 1.5:1 and wherein 0.4 to 1 part by weight of said alkali metal sesquisilicate are present for each part by weight of said activator.

14. The composition of claim 7 having a further content of from 0.05% to 1.5% by weight of optical brighteners.

15. In the process of washing textiles which comprises contacting said textiles with an aqueous solution containing an effective amount of a conventional washing agent containing a surface-active compound selected from the group consisting of anionic surface-active compounds, non-ionic surface-active compounds and amphoteric surface-active compounds, an inorganic percompound, an activator for said percompound, optical brighteners and alkaline-reacting builder salts, the improvement which consists in utilizing the composition of claim 1 as said activator for said percompound.

References Cited UNITED STATES PATENTS 3,637,339 1/1972 Gray 202 X 3,663,444 5/1972 Schmadel 20299 3,655,569 4/ 1972 Hellsten 252--99 3,650,962 3/1972 Werdehausen et al. 252186 3,630,921 12/1971 Disch et al. 25199 X 3,284,462 11/1966 Liechti et al 252-99 X FOREIGN PATENTS 1,059,601 1/ 1958 Germany 252-102 MAYER WEINBLATI, Primary Examiner US. Cl. X.R. 

